Anionic photochemical rearrangement of 3-hydroxypyran-4-ones bearing oxazol-2-one fragment.

The photochemical behavior of in situ generated anions of 3-hydroxypyran-4-ones containing an oxazol-2-one moiety was studied. For the first time, it was demonstrated that blue LED light irradiation (450 nm) of substituted 3-hydroxypyran-4-ones in the presence of a base leads regiospecifically to the formation of isomeric 3-hydroxypyran-2-ones. Transformation of the starting 3-hydroxypyran-4-ones into the corresponding anions is necessary for the presented photoprocess. Based on the considered visible light induced rearrangement, a general method for the synthesis of 3-hydroxypyran-2-ones with an oxazol-2-one moiety was elaborated. The structure of one of the synthesized compounds was confirmed by X-ray diffraction.

1,1'-Carbonyldiimidazole-mediated transformation of allomaltol containing hydrazides into substituted 3-acetyltetronic acids.

For the first time, the reaction of allomaltol containing hydrazides with 1,1'-carbonyldiimidazole (CDI) was studied. It was shown that under the considered conditions, 3-hydroxy-4-pyranone derivatives were transformed into 3-acetyltetronic acids bearing a pyrrolidin-2-one moiety. We have found that the key intermediates of the investigated process are substituted 6-oxa-1-azaspiro[4.5]dec-7-ene-2,9-diones. The structures of one final product and one intermediate were confirmed by X-ray analysis. The disclosed reaction was tested using a wide range of substituted allomaltols with various carboxamide units. It was demonstrated that in the case of hetaryl containing hydrazides and hydroxamic acids, the direction of the process is completely changed and cyclization into substituted pyrano[3,2-b]pyrans occurs.

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment.

For the first time, we elaborated a method for the synthesis of pyrimidines containing an allomaltol unit. The suggested approach is based on the reaction of 2-(1-(dimethylamino)-3-oxo-3-arylprop-1-en-2-yl)-3-hydroxy-6-methyl-4H-pyran-4-ones with cyanamide. The photochemical behavior of the obtained pyrimidines was investigated. It was shown that for the hydroxy derivatives the main pathway of phototransformation is a 6π-electrocyclization of the 1,3,5-hexatriene system and subsequent [1,9]-H sigmatropic shift leading to dihydrobenzo[h]pyrano[2,3-f]quinazolines. At the same time, for methylated analogues the photoreaction proceeds in two directions resulting in the formation of a mixture of the corresponding dihydrobenzo[h]pyrano[2,3-f]quinazolines and polyaromatic products. The obtained dihydro derivatives are stable compounds and do not undergo aromatization upon further UV irradiation. The structures of two of the dihydrobenzo[h]pyrano[2,3-f]quinazolines were confirmed by X-ray diffraction analysis. Based on the performed studies, a two-stage telescopic method for the synthesis of polyaromatic benzo[h]pyrano[2,3-f]quinazolines including the initial photocyclization of the starting pyrimidines and the final dehydration was proposed.

Photochemical synthesis and ring-chain-ring tautomerism of benzo[4,5]imidazo[1,2-a]cyclopenta[e]pyridines.

UV-mediated approach for the preparation of benzo[4,5]imidazo[1,2-a]cyclopenta[e]pyridine derivatives from allomaltols containing a benzimidazole fragment was developed. The suggested method includes ESIPT-induced contraction of a 3-hydroxypyran-4-one core and further intramolecular trapping of unstable α-hydroxy-1,2-diketone. The distinctive feature of the obtained photoproducts is ring-chain-ring tautomerism in solution. Based on X-ray analysis, the obtained photoproducts in the solid state exist in one isomeric form. Various types of derivatization of the synthesized compounds allow both forms of tautomers to be trapped.

A study of the photochemical behavior of terarylenes containing allomaltol and pyrazole fragments.

The photochemical properties behavior of 3-hydroxy-4-pyranone containing terarylenes with a pyrazole bridge fragment were studied. It was shown that UV-induced 6π-electrocyclization of the 1,3,5-hexatriene system was not observed for the considered objects molecules. At the same time, the phototransformation of such systems proceeds exclusively in the direction of the contraction of the pyranone ring leading to unstable α-hydroxydiketones. For the first time the possibility of isolation of the resulting α-hydroxydiketones in pure form was demonstrated. Wherein, it was shown that relatively low stable α-hydroxydiketones can be trapped by reaction with 1,2-phenylenediamine. The general method for the preparation of the corresponding quinoxalines on the basis of the aforementioned condensation was implemented. It was demonstrated that the studied photoreaction does not depend on the type of pyrazole bridge. The structures of three of synthesized products were established by X-ray diffraction.

Photoinduced assembly of the 3,4,4a,7a-tetrahydro-1H-cyclopenta[b]pyridine-2,7-dione core on the basis of allomaltol derivatives.

A novel photochemical method for the construction of previously unknown substituted 4a,7a-dihydroxy-5-methyl-3,4,4a,7a-tetrahydro-1H-cyclopenta[b]pyridine-2,7-diones based on readily available allomaltol derivatives containing an amide group was established. The proposed approach includes the photoinduced contraction of an allomaltol ring and the subsequent intramolecular cyclization of an unstable α-hydroxy-1,2-diketone intermediate. For the first time we have shown the use of a side chain amide function as a trapping element for the final cyclization of photogenerated α-hydroxy-1,2-diketones. The structures of two synthesized photoproducts were determined by X-ray diffraction.

Photoinduced 6π-Electrocyclization of a 1,3,5-Hexatriene System Containing an Allomaltol Fragment.

For the first time, the possibility of photocyclization of the 1,3,5-hexatriene system containing a fragment of allomaltol was demonstrated. A preparative method for the synthesis of previously unknown benzo[5,6]chromeno[8,7-d]oxazole-2,7(3H)-diones was developed based on the investigated photoreaction. A distinctive feature of this approach is the modification of the starting terarylenes aimed at blocking the competitive process leading to side reactions of the pyranone fragment. It was shown that the proposed photocyclization of substituted oxazol-2-ones can be used for the photogeneration of biologically active alcohols and various acids. The structure of one of the cyclization products was determined by X-ray diffraction.

Construction of Spiro-γ-butyrolactone Core via Cascade Photochemical Reaction of 3-Hydroxypyran-4-one Derivatives.

We elaborate a novel one-step photochemical method for the synthesis of spiro-γ-butyrolactone derivatives from 3-hydroxypyran-4-ones. The suggested approach is based on a cascade process including initial photoinduced contraction of 4-pyranone ring followed by intramolecular cyclization leading to the final spiro system. A distinctive feature of the proposed method is intramolecular trapping of unstable α-hydroxydiketone intermediate formed in situ as a result of a photochemical reaction. The structures of two synthesized 1-oxaspiro[4.4]non-8-ene-2,6,7-triones were determined by X-ray diffraction.

Synthesis of substituted naphtho[1,2-b]benzofuran-7(8H)-ones via photoinduced rearrangement of 4H-chromen-4-one derivatives.

A simple and efficient method was developed for the synthesis of substituted naphtho[1,2-b]benzofuran-7(8H)-ones based on the photorearrangement reaction of 4H-chromen-4-one derivatives. The studied reaction includes the photocyclization of the hexatriene system, [1,9]-H-sigmatropic rearrangement and heterocyclic ring opening. The starting terarylenes were prepared via a new three-component tandem condensation of 3-(dimethylamino)-1-(2-hydroxyaryl)prop-2-en-1-ones, arylglyoxals and cyclic 1,3-diketones.

One-pot synthesis of substituted pyrrolo[3,4-b]pyridine-4,5-diones based on the reaction of N-(1-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-2-oxo-2-arylethyl)acetamide with amines.

The condensation of primary amines with N-(1-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-2-oxo-2-arylethyl)acetamides was explored. Thus, a previously unknown recyclization of the starting material was observed in acidic ethanol in the presence of an amine, which provided the corresponding dihydropyrrolone derivative as the major reaction product. Based on this transformation, a practical and convenient one-pot synthetic method for substituted pyrrolo[3,4-b]pyridin-5-ones could be devised.